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Competitive formation of molecular inclusion complexes of chlordecone and β-hexachlorocyclohexane with natural cyclodextrins: DFT and molecular dynamics study

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Abstract

Context

Chlordecone (CLD) and β-hexachlorocyclohexane (β-HCH) are chlorinated pesticides that coexist as persistent organic pollutants in the groundwater of several countries in the Caribbean, being an environmental issue. This work evaluates theoretically the competitive formation of host–guest complexes pesticides@cyclodextrines (CDs) as an alternative for water purification and selective separation of pesticides.

Methods

Quantum mechanical calculations based on density functional theory (DFT) and classical molecular dynamics (MD) simulations were used to achieve information on geometries, energies, structure, and dynamics of guest–host complexes in the gas phase, implicit solvent medium, and in aqueous solutions.

Results

DFT studies showed that interactions of both pesticides with CDs are mediated by steric factors and guided by maximization of the hydrophobic interactions either with the other pesticide or with the CD cavity’s inner atoms. MD results corroborate the formation of stable complexes of both pesticides with the studied CDs. α-CD exhibited a preference for the smaller β-HCH molecule over the CLD that could not perturb the formed complex.

Conclusions

The simulation of competitive formation with γ-CD illustrated that this molecule could accommodate both pesticides inside its cavity. These results suggest that CDs with smaller cavity sizes such as α-CD could be used for selective separation of β-HCH from CLD in water bodies, while γ-CD could be used for methods that aim to remove both pesticides at the same time.

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Data sharing does not apply to this article as no datasets were generated or analyzed during the current study.

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Acknowledgements

Computational calculations were performed using Wahoo, the cluster of the Centre Commun de Calcul Intensif of the Université des Antilles, Guadeloupe, France. The authors wish to thank Raphael Pasquier, Jacques Laminie and Pascal Poullet for their support with the calculation facilities. The Informatics service of InSTEC at Havana, Cuba, is also gratefully acknowledged. Babak Minofar acknowledges the access to computational resources provided by the CESNET LM2015042 and the CERIT Scientific Cloud LM2015085, provided under the program “Projects of Large Research, Development, and Innovations Infrastructures”. This work was financially supported by the project CIMPest (CBA-330810-2018-P-1, INTEC, Dominican Republic), the project DetDePest (CAPES, Guadeloupe), and project TATARCOP (InSTEC, Cuba). We thanks the valuable help of Dr. David Reha, University of South Bohemia, during last revision of the manuscript.

Funding

This work was supported by the project CIMPest (CBA-330810–2018-P-1, INTEC, Dominican Republic), the project DetDePest (CAPES, Guadeloupe), and project TATARCOP (InSTEC, Cuba).

Author information

Authors and Affiliations

  1. Department of Chemistry, KU Leuven, B-3001, Louvain, Belgium

    Anthuan Ferino-Pérez

  2. Instituto Tecnológico de Santo Domingo (INTEC), Avenida de los Próceres #49, Los Jardines del Norte 10602, Santo Domingo, Dominican Republic

    Queiroz Portorreal & Ulises J. Jaúregui-Haza

  3. Laboratory of Inorganic Chemistry (LAC), Department of Chemistry and Applied Biosciences (D-CHAB), Federal Institute of Technologies (ETH), Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland

    Juan J. Gamboa-Carballo

  4. Department of Chemistry, Faculty of Science, University of South Bohemia in Ceske Budejovice, Branisovska 31, 370 05, Ceske Budejovice, Czech Republic

    Babak Minofar

  5. Laboratoire COVACHIMM2E EA 3592, Université des Antilles, BP 250, Pointe à Pitre Guadeloupe (FWI), France

    Sarra Gaspard

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  1. Anthuan Ferino-Pérez
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  6. Ulises J. Jaúregui-Haza
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Contributions

Conceptualization: Anthuan Ferino-Pérez, Babak Minofar, Ulises J. Jaúregui-Haza; Data curation: Anthuan Ferino-Pérez, Queiroz Portorreal, Juan J. Gamboa-Carballo, Babak Minofar; Formal analysis: Anthuan Ferino-Pérez, Babak Minofar, Sarra Gaspard, Ulises J. Jaúregui-Haza; Funding acquisition [Sarra Gaspard, Ulises J. Jaúregui-Haza; Investigation: Anthuan Ferino-Pérez, Queiroz Portorreal, Juan J. Gamboa-Carballo, Babak Minofar; Methodology: Anthuan Ferino-Pérez, Babak Minofar, Ulises J. Jaúregui-Haza; Project administration: Ulises J. Jaúregui-Haza; Resources: Babak Minofar, Sarra Gaspard, Ulises J. Jaúregui-Haza; Software: Anthuan Ferino-Pérez, Juan J. Gamboa-Carballo, Babak Minofar; Supervision: Babak Minofar, Sarra Gaspard, Ulises J. Jaúregui-Haza; Visualization: Anthuan Ferino-Pérez, Babak Minofar; Writing – original draft: Anthuan Ferino-Pérez, Babak Minofar, Ulises J. Jaúregui-Haza; Writing – review & editing: Juan J. Gamboa-Carballo, Sarra Gaspard, Ulises J. Jaúregui-Haza.

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Correspondence to Ulises J. Jaúregui-Haza.

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Ferino-Pérez, A., Portorreal, Q., Gamboa-Carballo, J.J. et al. Competitive formation of molecular inclusion complexes of chlordecone and β-hexachlorocyclohexane with natural cyclodextrins: DFT and molecular dynamics study. J Mol Model 29, 196 (2023). https://doi.org/10.1007/s00894-023-05600-w

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